Phenolic condensation product and method of making the same.



UNITED STATES PATENT oFFIoEJ LEO H. BAEKELAND, OF YONKEBS, AND NATHANIEL THURLOW, OF

ASSIG-NORS TO GENERAL-BAKELITE CO TION OF NEW YORK.

PHZENOLIC CONDENSATION PRODUCT AND METHOD OF MAKING THE SAIME.

No Drawing.

I To all whom it may concern Be it known that we, (1) LEO H. BAEKn- LAND and (2) NATHANIEL THURLOW, citizens of the United States, residing at (1) Yonkers and (2) New York, in the counties of (1) Westchester and (2) New York, State of New York, have invented certain new and useful Improvements in Phenolic Condensation Products and Methods of Making the Same, of which the following is a specification.

For the preparation of insoluble, infusible phenolic condensation products, several methods are known, involving the reaction of hexamethylenetetramin, or of mixtures of formaldehyde and ammonia which are equivalent to hexamethylenetetramin, upon phenols, or upon oxybenzyl-alcohols, such as saligenin, or upon dehydration products thereof, as for instance the so-called fusible, resinous phenol-formaldehyde condensation products variously known as saliretins, phenol resins, shellac substitutes, novolak, etc.

In all such methods, considerable amounts of ammonia are set free. This abundant evolution of ammonia :exaggerates the tendency of the mass to foam when subjected to the hardening process under the influence of heat, and may give rise to porous final products, which are defective for most purposes. Such foaming or porosity may be avoided by applying a suitable counterpressure during the act of heating, in which case considerable free ammonia remains in the mass.

The present invention relates to methods of preparing phenolic condensation prodnets in such manner as to avoid or diminish the objectionabove -mentioned, and also to the products formed in the practice of such methods.

According to the present invention, we substitute for a part or all of the hexamethylenetetramin which as is well known is an organic'base, a suitable salt of this base, for instance hexamethylenetetraminhydrochlorid, sulfate, tartrate, oxalate, etc. By proce'eding in this manner a considerable portion of the ammonia, which would otherwise be set free, combines with the hydrochloric acid or with other acid entering into the constitution of the salt, form' a corresponding ammonium salt, which, 1n the case of hexamethylenetetraminhydrochlorid, is

Specification of Letters Patent.

Patented June 13, 1916.

Application filed December 11, 1912. Serial No. 736,214.

chlorid of ammonium. The new method presents also the additional advantage that the hardening by application of ,heat is decidedly quickened, as compared with the use of hexamethylenetetramin.

The invention will be explained by reference to certain illustrative embodiments thereof, it being understood that the in ventlon is not restricted to these examples,

NEW YORK, N. Y., MPANY, OF NEW YORK, .N. Y., A CORPORA- or to the specific proportions and conditions therein disclosed as preferable.

Example I: 140 grams of phenol, or the chemically equivalent proportion of the homologues of phenol, is mixed with 47 grams of hexamethylenetetraminhydrochlorid, and the mixture heated toapproximately 110 C. A reaction sets in, accompanied by foaming and thickening of the mass and evolution of ammonia. At this stage the product may be dissolved in suitable solvents, as for instance acetone, alcohol, amylacetate, and the like, or preferably in mixtures of these solvents, yielding therewith varnishes or lacquers which may be applied and baked on in the manner now well understood in the art. Or the mass resulting from this; first reaction, without addition of solvent liquids, may jected to further heating preferably in suitable molds and under pressure. Application of an increased temperature willsoon harden the product to the infusible and insoluble state. A suitable temperature is, for instance, 160 0., although lower or higher temperatures may used. The propor tions of 'hexamethylenetetramin salt and phenol may be varied within the reasonable limits in which the same technical eifects are obtainable, the use of unnecessarily able manner a fusible, soluble, resinous phebe subcondensation product jected to heat,'suitable conditions being as described under Example, I.

It is to be understood that suitable comminuted filling materials may be added as required, as Well as other substances serving to improve the physical or chemical qualities of the final product or of the original'reacting'materials. For instance, we may add solid, semi-liquid or liquid materials of the character described in U. S.

Patent No. 942,699, patented December 7,

1909, to L. H. Baekeland, such additions serving to reduce the brittleness of the final product, or to improve the plasticity thereof by acting as solid solvents therefor or other- :wise. Instead of phenol, other suitable phenolic bodies, as for example the homologues of phenol, may be used. Similarly, instead of formaldehyde or hexamethylenctetraminhydrochlorid, we may use the equivalents of these substances.

Instead of carrying out the reaction in a continuous operation, the reaction may be interrupted at suitable times in order to obtain products which are still fusible and soluble, and can be kept in stock or sold in the trade, such products being employed at a later period for the purposes of this invention. For example, such soluble condensation products may be dissolved in suitable solvents for the preparation of var- "nishes or lacquers, or used for molding purposes, as plastics,either alone or in conjunction with such suitable filling materials as wood fiber, asbestos and the like. The transformation into the final product can be brought about when and under the conditions desired by the application of heat, or better by the joint application of heat and pressure. Inasmuch as the use of the salt of hexamethylenetetramin has for its object the limitation of the production of free ammonia, it will be understood. that this favorable action may be supplemented as desired by the use of other substances having a tendency to fix the free ammonia, as for example solid organic anhydrids.

In the claims, the term, phenolic body is used to designate not only phenol and its homologues, but also such soluble, fusible phenolic condensation products as are referred to under Example II. The term phenolic condensation products is intended to include both the infusible and insoludensation products.

ble, and also the fusible andsoluble .con-

The expression a phenol 1s used to include the homologues of phenol, and mixtures containing the same.

We claim: 1 1. The method of making phenolic condensation products, which consists in reacting upon a phenolic body with a salt of hex- 4. The method of making phenolic condensation products, which consists in reacting upon a phenol with hexamethylenetetraminhydrochlorid.

As a new composition of matter, a mixture containin a phenolic body and a salt of hexamethy enetetramin, said mixture transformable by heat into an infusible, insoluble body.

6. As a new composition of matter, a mixture containing a henolic body andhexamethylenetetramin ydrochlorid, said mixture transformable by heat into an infusible, insoluble body.

'7. The herein-described composition of matter, containing a fusible phenolic condensation product and a salt of hexamethylenetetramin, said composition transformable by heat into an infusibleand insoluble body.

8. The herein-described composition of matter, containing a fusible phenolic condensation product and hexamethylenetetraminhydrochlorid, said composition transformable by heat into an infusible and insoluble body.

10. The herein-described amorphous phenolic condensation'product resulting from the reaction between a phenolic body and hexamethylenetetraminhydrochlorid, said product characterized by the presence there-.

in of ammonium chlorid.

In testimony whereof, we aflix our signatures in presence of two witnesses.

LEO H. BAEKELAN D. NATHAN TEL THURLOW.

Witnesses:

HERBERT S. MAY, CHARLES B. MORTON. 

